The electric charge distribution of molecules such as H₂ and D₂ is inversion-symmetric so that permanent dipole moments do not exist: such molecules are infrared-inactive. It is therefore interesting that gaseous, liquid, and solid hydrogen and its isotopes actually absorb infrared radiation, for example if gas densities are sufficiently high. The observed absorption arises from electric dipole moments induced by intermolecular interactions. It is of a supermolecular origin, due to binary (or higher-order) molecular complexes that may be transient (i.e., in a collisional encounter) or relatively stable (van-der-Waals molecule). Interaction-induced electric dipoles arise from the same mechanisms that generate the intermolecular forces: exchange forces, dispersion forces, and multipolar induction. Recently the induced dipole and potential energy surfaces of H₂ pairs have been obtained by advanced quantum-chemical calculations. Interaction-induced absorption, more commonly called collision-induced absorption (CIA), by H₂ pairs is an important opacity source in the atmospheres of various types of planets and cool stars, such as late stars, low-mass stars, brown dwarfs, certain white dwarfs, etc., and therefore of special astronomical interest. The emission spectra of cool white dwarf stars differ significantly from the expected blackbody spectra of their cores, mainly due to collision-induced absorption by collisional complexes of hydrogen and helium in the stellar atmospheres. Before proceeding to the frequencies and temperatures of interest it is good to check the new potential energy surface and induced dipole surface in all possible ways by comparison with existing isotopic laboratory measurements. Furthermore, the new potential energy surface is directly compared with previously available, well established intermolecular potential energy surfaces. The electric charge distributions of deuterium and hydrogen are very similar. The new potential energy and induced dipole surfaces were originally obtained to facilitate the computation of the collision-induced absorption of hydrogen. However, by replacing the rotovibrational wavefunctions of H₂ with those of D₂ the surfaces can also be used to calculate the collision-induced absorption of deuterium pairs, thereby probing them further. At the temperature of 298K existing measurements of the collision-induced absorption of D₂--D₂ gas are compared with our quantum scattering calculations in the D₂ fundamental band (approximately 2,500cm⁻¹ to 4,500cm⁻¹). Furthermore, measurements of the collision-induced absorption of deuterium (D₂) in the D₂ first overtone band (about 5,250cm⁻¹ to 7,250cm⁻¹) at 201K are reported. These measurements are compared with ab initio calculations of the absorption spectra. Close agreement of measured and calculated spectra is seen.
| Identifer | oai:union.ndltd.org:UTEXAS/oai:repositories.lib.utexas.edu:2152/ETD-UT-2010-08-1960 |
| Date | 03 January 2011 |
| Contributors | Frommhold, Lothar |
| Source Sets | University of Texas |
| Language | English |
| Detected Language | English |
| Type | thesis, text |
| Format | application/pdf |
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